CN114907755B - Preparation method of visible light-induced self-repairing coating based on two-dimensional titanium carbide - Google Patents
Preparation method of visible light-induced self-repairing coating based on two-dimensional titanium carbide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2003/0806—Silver
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/085—Copper
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Abstract
The invention discloses a preparation method of a visible light-induced self-repairing coating based on two-dimensional titanium carbide, which is compounded by self-repairing aqueous polyurethane resin, a stabilizer, a leveling agent and a defoaming agent, wherein a modified two-dimensional titanium carbide material (MXene) is added as a visible light inducer in the self-making process of the self-repairing aqueous polyurethane resin, and the problem of degradation of the MXene which is an efficient photo-thermal conversion material in an aqueous system is effectively solved. Under the action of visible light, the visible light inducer at the coating parting generates heat through illumination to trigger physical and chemical reactions in the coating, so that the gap at the parting is closed, cracks disappear, the physical barrier effect of the coating is restored, and the ultra-strong self-repairing capability is realized. The paint has the advantages of no toxicity, incombustibility, safe use, good self-repairing performance under visible light and the like, and is an environment-friendly self-repairing paint with no toxicity and pollution.
Description
Technical Field
The invention relates to a preparation method of a coating, in particular to a preparation method of a visible light induced self-repairing aqueous polyurethane coating based on two-dimensional titanium carbide; belonging to the technical field of novel materials.
Background
The paint can protect, decorate, insulate and prevent corrosion to the object, and is widely used in various fields, and it is called five-large synthetic material together with plastics, synthetic rubber, synthetic fiber and adhesive. However, volatile Organic Compounds (VOCs) are generated during the production, use and processing of the coating, which cause a degree of damage to the atmosphere and to the health of humans. The VOC content of the aqueous paint is not high, and from the viewpoint of environmental protection, the aqueous paint is considered as one of the most potential paints in the paint industry, which has high solid content and gloss, low viscosity, and uses water as a dispersion medium, so that the aqueous paint is friendly to the environment and gradually replaces solvent-type paints.
However, aqueous coatings inevitably produce imperceptible microcracks and damage within the material during manufacture and use, and the spread and coalescence of these microcracks and damage can cause material failure, reducing the durability and reliability of the product. In order to solve the problem, scientists propose a concept of self-repairing materials, and the self-repairing of the materials is realized by means of adding repairing agents or externally stimulating functional groups.
The invention patent application number 202010748076.8 discloses a water-based polyurethane coating composition with self-repairing property, which comprises the following components in percentage by weight: (a) 35 to 50wt% of polyisocyanate; (b) 15-20 wt% of polyol; (c) 5-10wt% of dimethylolpropionic acid; (d) 3-8wt% of nano Co particle modified polyurethane microcapsule; the balance of water. The self-repairing waterborne polyurethane coating composition can excite the quick rupture of the microcapsules when the coating layer is ruptured, so that the self-repairing sensitivity is improved, the self-repairing process is accelerated, the performance degradation of the coating film is avoided, and the quality of the coating film is ensured.
The invention patent with application number 202010521143.2 discloses a self-repairing aqueous polyurethane coating, which comprises, by weight, 60-80% of polyurethane coating base liquid and 20-40% of self-repairing composite nanofibers, wherein the self-repairing composite nanofibers have a three-layer structure, and an inner core material, an intermediate barrier layer and an outer acrylate monomer are sequentially arranged from inside to outside. The self-repairing composite nanofiber uses silane as a core material, and on one hand, the silane has a crosslinking property, and can react with an acrylic ester monomer of an outer layer and be crosslinked and cured; on the other hand, the obtained crosslinked network can be subjected to reversible reaction at high temperature to obtain planetary silane molecules again, and the silane molecules are crosslinked and cured again after cooling, so that the coating layer is self-repaired again.
However, the self-repairing coating disclosed in the prior art has limited self-repairing times, and needs high temperature to have self-repairing effect, and is difficult to achieve for the coating used at normal temperature. In view of the above, the prior art needs to be innovated and improved, and proper materials are adopted, and through reasonable formula design and production process, the stability and the service performance of the water-based paint are ensured, and the water-based paint can realize self-repairing under the action of visible light after cracking, thereby meeting the requirements of industrial production, saving energy consumption and achieving the purpose of carbon emission reduction.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides a preparation method of a visible light-induced self-repairing type water-based polyurethane coating, which aims to solve the problems of high toxicity, flammability, poor use safety, environment pollution, poor self-repairing performance of the water-based coating, less self-repairing times, high energy consumption and the like of the oil-based coating in the prior art.
In order to achieve the above object, the present invention adopts the following technical scheme:
the invention firstly discloses a preparation method of a visible light-induced self-repairing coating based on two-dimensional titanium carbide, which comprises the following steps:
s1, preparing self-repairing aqueous polyurethane resin:
(1) Adding a polyol oligomer into a reactor provided with a stirrer, a thermometer and a reflux condenser, stirring, vacuumizing and dehydrating for 1-2 hours at 105-120 ℃, adding diisocyanate when the temperature is reduced to 60 ℃, reacting for 1-2 hours at 70-90 ℃, then adding a compound containing hydrophilic groups, bis (2-hydroxyethyl) disulfide and a low molecular polyol chain extender according to the quantity ratio of functional group substances, namely-NCO/-OH=1.2-1.6, and continuing to react for 2-4 hours to obtain a polyurethane prepolymer;
(2) Cooling the prepared polyurethane prepolymer to room temperature, adding triethylamine to neutralize carboxylate in the polyurethane prepolymer into salt, wherein the neutralization degree is 80-110%;
(3) Discharging the neutralized prepolymer into a disperser, adding 1-3 parts by mass of visible light inducer for reaction for 1-2 hours, adding deionized water for dispersion under stirring, and then adding excessive low-molecular fatty amine chain extender for reaction for 10-30 minutes to obtain self-repairing aqueous polyurethane resin;
s2, preparing a visible light induced self-repairing environment-friendly coating:
and (2) placing 100 parts by mass of the self-repairing aqueous polyurethane resin prepared in the step (S1) in a stirrer, adding 0.2-1 part by mass of stabilizer, 0.1-0.3 part by mass of flatting agent and 0.1-0.5 part by mass of defoamer into the stirrer, and fully stirring to uniformly mix the components to obtain the visible light-induced self-repairing environment-friendly coating.
Preferably, the carboxyl group content in the polyurethane prepolymer is 0.7-2.0% by mass.
Preferably, the aforementioned visible light inducer is modified MXene, and the preparation method is as follows: dissolving 10 parts by mass of lithium fluoride in 100 parts by mass of 9mol/L hydrochloric acid to completely dissolve the lithium fluoride to form a mixed solution; then 5-10 parts by mass of Ti 3 AlC 2 Adding ceramic powder into the mixed solution, and stirring at 25-35 ℃ for reaction for 24-48h; washing with deionized water for 5-10 times after the reaction is completed, and drying to obtain an intermediate product; finally, 10 parts by mass of intermediate product, 1-2 parts by mass of nano metal powder and 20-50 parts by mass of intercalation agent are taken and stirred for 12-24 hours at 25-35 ℃ to obtain the visible light inducer. MXene is a high-efficiency photo-thermal conversion agent, but has the problem of degradation in water, and is still an important research subject in basic research to date. In the self-making process of the visible light inducer, nano metal powder is particularly added and inserted by an intercalation method, so that on one hand, the dispersion effect can be improved, the photo-thermal conversion effect is optimized, and in addition, the stability of the visible light inducer in the water-based paint can be improved. Compared with other visible light inducers in the prior art, the self-made MXene has the advantages of high photo-thermal conversion efficiency, so that the self-repairing performance of the coating can be optimized; meanwhile, as the inorganic nano filler, the material strength can be improved, and the application of the visible light inducer can further improve the conductivity of a coating film formed after the self-repairing coating material is volatilized, so that the volume resistivity of the coating film is greatly reduced.
Still preferably, the nano metal powder is one or a mixture of a plurality of nano gold powder, nano silver powder and nano copper powder.
Still preferably, the intercalating agent is one or more of dimethyl sulfoxide, dimethylformamide and dimethylacetamide.
More preferably, the polyol oligomer is one or more of polyester diol, polyether diol, polytetrahydrofuran diol and polycarbonate diol; the diisocyanate is one or a mixture of more of toluene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
Further preferably, the compound containing a hydrophilic group is one or more of dimethylolpropionic acid and dimethylolbutyric acid; the low molecular polyol chain extender is one of ethylene glycol, diethylene glycol and 1, 4-butanediol; the dosage of the low-molecular fatty amine chain extender is as follows: the excess of-NCO species upon reaction with the prepolymer is 50-70% and is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine.
Still more preferably, the aforementioned stabilizer is one or more of o-hydroxybenzophenone, o-hydroxyphenyl benzotriazole, phenyl salicylate, nickel dibutyldithiocarbamate, phosphite, 2, 6-di-t-butyl-p-cresol, pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], zinc dialkyldithiophosphate, zinc dialkyldithiocarbamate.
Still further preferably, the leveling agent is a polyorganosiloxane, a polyether-modified polyorganosiloxane, or a fluorosurfactant, and the antifoaming agent is an aqueous silicone antifoaming agent.
The invention has the advantages that:
(1) The self-repairing type coating is prepared based on self-made two-dimensional titanium carbide (MXene) and by adopting self-made self-repairing type aqueous polyurethane resin as a main raw material, is non-toxic and pollution-free environment-friendly, and has the advantages of non-toxicity, incombustibility, safe use, low carbon, self-repairing by visible light, repeated self-repairing and the like;
(2) According to the invention, the actual application requirement of the visible light-induced self-repairing environment-friendly coating is comprehensively considered, the problem of degradation of the MXene high-efficiency photo-thermal conversion material in a water-based system is effectively solved by modifying the visible light inducer of the two-dimensional material, meanwhile, the water-based polyurethane coating is endowed with good self-repairing capability, the visible light inducer at the coating parting is subjected to illumination heat generation under the effect of visible light to trigger physical and chemical reactions in the coating, so that the clearance closure and crack disappearance at the parting are realized, the physical barrier effect of the coating is recovered, and the self-repairing is realized;
(3) The leveling agent, the water-based defoaming agent, the stabilizer and other auxiliary agents are added into the paint, and the synergistic effect among the components endows the paint with better self-repairing capability, better processing and construction performances, greatly optimized adhesive force and weather resistance, better dispersion in water and good stability, and is also suitable for a water-based system. Therefore, the visible light-induced self-repairing environment-friendly paint can meet the use requirements of different environments, and has a wider application range.
Drawings
Fig. 1 a, b and c are graphs showing the effect of temperature change in visible light after the coatings of comparative example 1, example 1 and example 2 were formed into films, respectively;
FIG. 2 is a graph showing the effect of self-healing after the coating of example 1 has been formed into a film;
FIG. 3 is a graph showing the effect of self-healing after the coating of example 2 has been formed into a film;
FIG. 4 is a graph showing the effect of self-healing after the coating of example 3 has been formed into a film;
FIG. 5 is a graph showing the effect of self-repairing the coating of comparative example 1 after film formation.
Detailed Description
The invention is described in detail below with reference to the drawings and the specific embodiments.
Example 1
The coating of this example was prepared by the following method:
s0, preparing a visible light inducer: dissolving 10 parts by mass of lithium fluoride in 100 parts by mass of 9mol/L hydrochloric acid to completely dissolve the lithium fluoride; then, 5 parts by mass of Ti 3 AlC 2 Adding ceramic powder into the mixed solution, and reacting at 35 DEG CStirring for 24 hours; washing with deionized water for 10 times after the reaction is completed, and drying to obtain an intermediate product. Taking 10 parts by mass of intermediate product, 1 part by mass of nano gold powder and 20 parts by mass of dimethyl sulfoxide, and stirring for 24 hours at 25 ℃ to obtain the visible light inducer.
S1, preparing self-repairing aqueous polyurethane resin:
(1) Adding 40 parts by mass of polyester diol into a reactor provided with a stirrer, a thermometer and a reflux condenser, stirring, vacuumizing and dehydrating for 2 hours at 105 ℃, adding 10 parts by mass of toluene diisocyanate and 6 parts by mass of hexamethylene diisocyanate when the temperature is reduced to 60 ℃, heating to 70 ℃ for reacting for 1 hour, then adding 1.6 parts by mass of dimethylolbutyric acid, 1.5 parts by mass of bis (2-hydroxyethyl) disulfide and 0.9 part by mass of ethylene glycol, and continuing to react for 4 hours to obtain a polyurethane prepolymer;
(2) Cooling the prepared polyurethane prepolymer to room temperature, and adding 0.75 part by mass of triethylamine to neutralize the prepolymer into salt;
(3) Discharging the neutralized prepolymer into a disperser, adding 1 part by mass of the visible light inducer prepared in the step S1 for reaction for 2 hours, adding 86 parts by mass of deionized water under high-speed shearing for dispersing, and adding 0.74 part by mass of ethylenediamine for chain extension reaction for 30 minutes to obtain the self-repairing aqueous polyurethane resin.
S2, preparing a visible light induced self-repairing environment-friendly coating:
100 parts by mass of the self-repairing aqueous polyurethane resin prepared in the step S1 are placed in a disperser provided with an ultrasonic dispersing device, and then 0.1 part by mass of o-hydroxybenzophenone, 0.1 part by mass of o-hydroxyphenyl benzotriazole, 0.1 part by mass of polyorganosiloxane leveling agent and 0.1 part by mass of aqueous organosilicon defoaming agent are added into the disperser, and the components are fully stirred to be uniformly mixed, so that the visible light-induced self-repairing environment-friendly coating of the embodiment is prepared.
Example 2
The coating of this example was prepared by the following method:
s0, preparing a visible light inducer: dissolving 10 parts by mass of lithium fluoride in 100 parts by mass of 9mol/L hydrochloric acid to completely dissolve the lithium fluoride; then 7 parts by mass of Ti 3 AlC 2 Ceramic materialAdding the powder into the mixed solution, and reacting and stirring for 32 hours at 30 ℃; washing with deionized water for 8 times after the reaction is completed, and drying to obtain an intermediate product. 10 parts by mass of intermediate product, 1.5 parts by mass of nano silver powder and 30 parts by mass of dimethylformamide are taken and stirred at 30 ℃ for 16 hours, so as to obtain the visible light inducer.
S1, preparing self-repairing aqueous polyurethane resin:
(1) Adding 40 parts by mass of polyether glycol into a reactor provided with a stirrer, a thermometer and a reflux condenser, stirring, vacuumizing and dehydrating at 110 ℃ for 1.5 hours, cooling to 60 ℃, adding 14 parts by mass of xylylene diisocyanate, heating to 75 ℃ for reacting for 1.5 hours, then adding 2.3 parts by mass of dimethylolpropionic acid, 0.4 part by mass of bis (2-hydroxyethyl) disulfide and 0.2 part by mass of ethylene glycol, and continuing to react for 4 hours under stirring to obtain polyurethane prepolymer;
(2) Cooling the prepared polyurethane prepolymer to room temperature, and adding 1.7 parts by mass of triethylamine to neutralize the prepolymer into salt;
(3) Discharging the neutralized prepolymer into a disperser, adding 2 parts by mass of the visible light inducer prepared in the step S1 for reaction for 1h, adding 70 parts by mass of deionized water under high-speed shearing for dispersing, and adding 1.7 parts by mass of diethylenetriamine for chain extension reaction for 20 minutes to obtain the self-repairing aqueous polyurethane resin.
S2, preparing a visible light induced self-repairing environment-friendly coating:
100 parts by mass of the self-repairing aqueous polyurethane resin prepared in the step S1 are placed in a disperser provided with an ultrasonic dispersing device, and then 0.2 part by mass of nickel dibutyl dithiocarbamate, 0.3 part by mass of phosphite ester, 0.2 part by mass of polyether modified polyorganosiloxane leveling agent and 0.3 part by mass of aqueous organosilicon defoaming agent are added into the disperser, and the components are fully stirred to be uniformly mixed, so that the visible light induced self-repairing environment-friendly coating of the embodiment is prepared.
Example 3
The coating of this example was prepared by the following method:
s0, preparing a visible light inducer: 10 parts by mass of lithium fluoride was dissolved in 100 parts by mass of 9mol/L hydrochloric acid to completeDissolving; then, 10 parts by mass of Ti 3 AlC 2 Adding ceramic powder into the mixed solution, and reacting and stirring for 34 hours at 35 ℃; washing with deionized water for 10 times after the reaction is completed, and drying to obtain an intermediate product. Taking 10 parts by mass of intermediate product, 2 parts by mass of nano copper powder and 50 parts by mass of dimethylacetamide, and stirring for 12 hours at 35 ℃ to obtain the visible light inducer.
S1, preparing self-repairing aqueous polyurethane resin:
(1) Adding 40 parts by mass of polytetrahydrofuran dihydric alcohol into a reactor provided with a stirrer, a thermometer and a reflux condenser, stirring, vacuumizing and dehydrating for 1 hour at 120 ℃, cooling to 60 ℃, adding 15 parts by mass of 4,4 '-dicyclohexylmethane diisocyanate and 13 parts by mass of diphenylmethane-4, 4' -diisocyanate, heating to 80 ℃ for reacting for 1 hour, then adding 3 parts by mass of dimethylolpropionic acid, 0.7 part by mass of bis (2-hydroxyethyl) disulfide and 0.4 part by mass of 1, 4-butanediol, and continuing to react for 2 hours under stirring to obtain a polyurethane prepolymer;
(2) Cooling the prepared polyurethane prepolymer to room temperature, and adding 2.4 parts by mass of triethylamine to neutralize the prepolymer into salt;
(3) Discharging the neutralized prepolymer into a disperser, adding 3 parts by mass of the visible light inducer prepared in the step S1 for reaction for 2 hours, adding 87 parts by mass of deionized water under high-speed shearing for dispersing, and adding 4.9 parts by mass of tetraethylenepentamine for chain extension reaction for 10 minutes to obtain the self-repairing aqueous polyurethane resin.
S2, preparing a visible light induced self-repairing environment-friendly coating:
100 parts by mass of the self-repairing aqueous polyurethane resin prepared in the step S1 are placed in a disperser provided with an ultrasonic dispersing device, and then 1 part by mass of pentaerythritol ester stabilizer of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ], 0.3 part by mass of fluorine-containing surfactant and 0.5 part by mass of aqueous organosilicon defoamer are added into the disperser, and the components are fully stirred to be uniformly mixed, so that the visible light-induced self-repairing environment-friendly coating of the embodiment is prepared.
Comparative example 1
(1) Preparing aqueous polyurethane resin;
adding 40 parts by mass of polyester diol into a reactor provided with a stirrer, a thermometer and a reflux condenser, vacuumizing and dehydrating for 1h at 100 ℃, cooling to room temperature, adding 10 parts by mass of isophorone diisocyanate, 6.4 parts by mass of hexamethylene diisocyanate, heating to 70 ℃, reacting for 1h, adding 1.6 parts by mass of dimethylolbutyric acid and 1.3 parts by mass of ethylene glycol, and continuing to react for 4h under stirring to obtain a prepolymer;
then cooling to room temperature, and adding 0.75 part by mass of triethylamine to neutralize the prepolymer into salt;
discharging to a disperser, adding 101 parts by mass of deionized water under high-speed shearing, adding 1.85 parts by mass of ethylenediamine, carrying out chain extension reaction for 30 minutes, and discharging to obtain the aqueous polyurethane resin.
(2) Preparation of environment-friendly paint:
in a disperser with an ultrasonic dispersing device, 100 parts by mass of the prepared aqueous polyurethane resin, 0.1 part by mass of o-hydroxybenzophenone, 0.1 part by mass of o-hydroxyphenyl benzotriazole, 0.1 part by mass of polyorganosiloxane leveling agent and 0.1 part by mass of aqueous organosilicon defoaming agent are added, and stirred and uniformly mixed to prepare the environment-friendly coating.
Performance detection
The weather resistance, acid resistance and self-repairing performance of the inventive examples 1, 2 and comparative examples were tested as follows:
(1) Wet heat resistance (weather resistance):
the coating product is put into a humid heat aging box after being dried, the temperature is controlled at 45 ℃ and the relative humidity is 95 percent, and the defects of color change, bubbling, falling off and the like are observed after 7 days.
(2) 5% sulfuric acid (acid resistance):
the coating product is put into an aqueous solution with 5 percent of sulfuric acid concentration to be soaked for 24 hours after being dried, and the changes of color change, bubbling, falling off and the like are observed.
(3) Self-healing ability and number:
after the coating product is coated and dried, a small crack is cut on the surface of the coating, and self-repairing is carried out under visible light until the small crack disappears. After self-repairing, a small crack is cut at the same position, the operation is repeated, and whether the crack can be self-repaired or not is observed.
(4) Strength retention after self-repair:
test paint film tensile Strength before self-repair of delta 0 Tensile strength after self-repair was delta 1 Intensity retention = delta 1 /δ 0 *100％。
The test results are shown in Table 1 below:
| test item | Moisture and heat resistance | Resistant to 5% sulfuric acid | Number of self-repair | Post-self-repair strength retention/% |
| Example 1 | No bubble and no falling off | No change | > 8 times | 96 |
| Example 2 | No bubble and no falling off | No change | > 8 times | 93 |
| Example 3 | No bubble and no falling off | No change | > 8 times | 95 |
| Comparative example 1 | Shedding off | Shedding off | 0 | 0 |
TABLE 1 results of Performance test of examples 1-3 and comparative example 1
After photo-curing, the effect of the paint of the invention is proved to be obvious compared with the effect of the comparative example 1 on the ageing resistance, acid resistance and self-repairing performance (self-repairing times and strength retention rate) of the examples 1-3.
Fig. 1 a is a graph showing the effect of temperature change in visible light after film formation of comparative example 1, fig. 1 b is a graph showing the effect of temperature change in visible light after film formation of example 1, and fig. 1 c is a graph showing the effect of temperature change in visible light after film formation of example 3. As can be seen from the figures, the temperature rise of the visible light-induced self-repairing paint according to the embodiments of the present invention is remarkable under the effect of visible light.
Fig. 2 to 5 are graphs of self-repairing effects of the paints of examples 1 to 3 and comparative example 1 after film formation, respectively, and it can be seen from the graphs that in the self-repairing effect detection, the self-repairing effect of the visible light-induced self-repairing paints of examples 1 to 3 is good and the self-repairing can be repeated for many times, and the fine cracks almost disappear; the coating of comparative example 1 had little self-healing effect and no change in the fine cracks and before healing.
Applicant analysis because: the self-made two-dimensional titanium carbide (MXene) is added into the waterborne polyurethane, so that the degradation inhibition of the MXene can be effectively realized, and meanwhile, the waterborne polyurethane also has better self-repairing capability. Therefore, under the action of visible light, the visible light inducer at the coating parting generates heat through illumination to trigger physical and chemical reactions in the coating, so that the gap closure at the parting is realized, the crack disappears, the physical barrier effect of the coating is recovered, and the self-repairing is realized. The addition of auxiliaries such as a leveling agent, a water-based defoaming agent and the like can further play a synergistic effect, and the overall performance of the paint is optimized, so that the visible light-induced self-repairing environment-friendly paint can better meet the use requirements under different conditions.
In conclusion, the visible light-induced self-repairing coating based on the two-dimensional titanium carbide, which is produced by the invention, has excellent performance, good system compatibility, low raw material cost, high production efficiency, easy industrialization, wide application and no release of toxic solvents in the whole process, and is a nontoxic and pollution-free water-based polyurethane coating.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be appreciated by persons skilled in the art that the above embodiments are not intended to limit the invention in any way, and that all technical solutions obtained by means of equivalent substitutions or equivalent transformations fall within the scope of the invention.
Claims (7)
1. The preparation method of the visible light induced self-repairing coating based on the two-dimensional titanium carbide is characterized by comprising the following steps of:
s1, preparing self-repairing aqueous polyurethane resin:
(1) Adding a polyol oligomer into a reactor provided with a stirrer, a thermometer and a reflux condenser, stirring, vacuumizing and dehydrating for 1-2 hours at 105-120 ℃, adding diisocyanate when the temperature is reduced to 60 ℃, reacting for 1-2 hours at 70-90 ℃, then adding a compound containing hydrophilic groups, bis (2-hydroxyethyl) disulfide and a low molecular polyol chain extender according to the quantity ratio of functional group substances, namely-NCO/-OH=1.2-1.6, and continuing to react for 2-4 hours to obtain a polyurethane prepolymer;
(2) Cooling the prepared polyurethane prepolymer to room temperature, adding triethylamine to neutralize carboxylate in the polyurethane prepolymer into salt, wherein the neutralization degree is 80-110%;
(3) Discharging the neutralized prepolymer into a disperser, adding 1-3 parts by mass of visible light inducer for reaction for 1-2 hours, adding deionized water for dispersion under stirring, and then adding excessive low-molecular fatty amine chain extender for reaction for 10-30 minutes to obtain self-repairing aqueous polyurethane resin;
the visible light inducer is modified two-dimensional titanium carbide MXene, and the preparation method comprises the following steps: dissolving 10 parts by mass of lithium fluoride in 100 parts by mass of 9mol/L hydrochloric acid to completely dissolve the lithium fluoride to form a mixed solution; then 5-10 parts by mass of Ti 3 AlC 2 Adding ceramic powder into the mixed solution, and stirring at 25-35 ℃ for reaction for 24-48h; washing with deionized water for 5-10 times after the reaction is completed, and drying to obtain an intermediate product; finally, 10 parts by mass of intermediate product, 1-2 parts by mass of nano metal powder and 20-50 parts by mass of intercalation agent are taken and stirred at 25-35 ℃ for reaction for 12-24 hours, so as to obtain a visible light inducer; the nanometer metal powder is one or a mixture of more of nanometer gold powder, nanometer silver powder and nanometer copper powder; the intercalation agent is one or a mixture of more of dimethyl sulfoxide, dimethylformamide and dimethylacetamide;
s2, preparing a visible light induced self-repairing environment-friendly coating:
and (2) placing 100 parts by mass of the self-repairing aqueous polyurethane resin prepared in the step (S1) in a stirrer, adding 0.2-1 part by mass of stabilizer, 0.1-0.3 part by mass of flatting agent and 0.1-0.5 part by mass of defoamer into the stirrer, and fully stirring to uniformly mix the components to obtain the visible light-induced self-repairing environment-friendly coating.
2. The method for preparing the two-dimensional titanium carbide-based visible light-induced self-repairing coating according to claim 1, wherein the mass content of carboxyl groups in the polyurethane prepolymer is 0.7-2.0%.
3. The method for preparing the two-dimensional titanium carbide-based visible light induced self-repairing coating according to claim 1, wherein the polyol oligomer is a mixture of one or more of polyester diol, polyether diol and polycarbonate diol; the diisocyanate is one or more of toluene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
4. The method for preparing a two-dimensional titanium carbide-based visible light-induced self-repairing coating according to claim 1, wherein the compound containing a hydrophilic group is a mixture of one or more of dimethylolpropionic acid and dimethylolbutyric acid; the low molecular polyol chain extender is one of ethylene glycol, diethylene glycol and 1, 4-butanediol; the low-molecular fatty amine chain extender is selected from one or a mixture of more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
5. The method for preparing a two-dimensional titanium carbide based visible light induced self-repairing coating according to any of claims 1 to 4, wherein the stabilizer is one or more of o-hydroxybenzophenone, o-hydroxyphenyl benzotriazole, phenyl salicylate, nickel dibutyldithiocarbamate, phosphite, 2, 6-di-tert-butyl-p-cresol, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester.
6. The method for preparing a two-dimensional titanium carbide based visible light induced self-repairing coating according to any of claims 1 to 4, wherein the leveling agent is a polyorganosiloxane or a fluorosurfactant.
7. The method for preparing a two-dimensional titanium carbide based visible light induced self-healing coating according to any of claims 1 to 4, wherein the defoamer is an aqueous silicone defoamer.
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| CN116218344B (en) * | 2023-03-31 | 2024-05-24 | 中国科学院长春应用化学研究所 | Surface repairing agent for water-based inflatable structural material, and preparation method and application thereof |
| CN116694219A (en) * | 2023-04-06 | 2023-09-05 | 江苏苏博特新材料股份有限公司 | Visible light-induced MXene/waterborne polyurethane antibacterial self-repairing composite coating and preparation method thereof |
| CN116218345B (en) * | 2023-04-19 | 2024-04-26 | 中国海洋大学 | Preparation method and application of photo-thermal nano heterojunction and self-repairing anticorrosive paint thereof |
| CN117384503B (en) * | 2023-10-13 | 2024-05-10 | 青岛恩泽化工有限公司 | Preparation method and application of efficient slow-release anti-flash rust agent |
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